Sulphocarboxylic esters



Patented July 18,1939

SULPHOCARBOXYLIC ESTERS Benjamin B. Harris, Chicago, Ill.

No Drawing.

Application November 15, 1937,

ScrialNo. 174,655 g 26 Claims. (01.260-400) My invention relates to a new class of chemical substances, and more in particular to a new class of chemical substances particularly adapted for use as detergents, wetting, penetrating,

emulsifying, lathering flotation and anti-spat- I tering agents, and for frothing purposes.

In certain classes of industries, there is a need for a certain class of chemical substances usually ,used in relatively small quantities but capable of use in larger quantities to secure aneffect principally the result of a wetting action such as at a water-oil interface. In the textile and dyeing industries, for example, there are many situations where a wetting or detergent act on is imperative as, for example, in launde ing, bleaching, mercerizing, dyeing or other operations, and many *difierent chemical substances have been produced calculated to reduce surface tension and promote wetting in these industries. The use of prior art substances has not been attended with unqualified success in all instances. Incertain other types of industries, such as the margarine industries, for example, problems in preventing the spattering of margarlne in frying have arisen. These problems are considered by some investigators as entirely a matter of wetting; in other words, by promoting greater attraction between the oleaginous and aqueous portions of the emulsion at the interfaces thereof. Although the problem is probably not one of wetting action entirely, it

appears that certain compounds which in theory tendto concentrate at the water-oil interface have an efiect upon the spattering behavior of margarine. This problem is discussed and a remedy disclosed in my prior .Patent Nos. 1,917,250 and 1,917,256. 7 I,

The principal object of my present invention is the provision of a new class of chemical substances capable of satisfactory use in connection with the problems'hereinabove discussed.

Another object is the provision of a new class of chemical substances which are in general of, relatively simple structure and can be cheaply made in commercial quantities.

Another object is the provision of a class of chemical substances of the character set forth which in the main'will be innocuous and nontoxic, -even-though employed in such foods margarine. v

Another object is the provision of a new class of chemical substances having improved wetting characteristics.

Other' objects and features of the invention will be apparent from a consideration of the following detailed description.

The substances of my invention are in general ester derivatives of lower molecular weight fatty acids with at least one unesterified sulphonic I acid group in the fatty acid radical wherein the group esterified with the fatty acid has a lipophile radical with at least four carbonatoms.

In certain circumstances there may be more than one unesterified sulphonic acid group in the fatty acid radical or there may be sulphonic acid groups that are esterified and other sulphonic acid groups that are not esterified, but in all cases there must be at least one unesterified sulphonic acid group in the fatty acid radical. The fatty acid radical with the free sulphonic acid group is of relatively low molecular weight and should contain not more than eight carbons.

Considering the compounds from another aspect, the molecule in each instance contains a lipophile group having at least four carbon atoms and a relatively low molecular weight hydrophile group which, in the class of compounds to which my present invention relates,-

" are sulpho-carboxylic or sulpho-fatty acid radicals. From still another angle, the compounds may be considered as combinations of a lipophile group having at least four carbon atoms and a relatively low molecular weight sulpho-carboxylic or sulpho-fatty acid group. A more complete understanding of what may comprise the lipophile group and the particular character of the sulpho-carboxylic or sulpho-fatty acid group will be had as the detailed description progresses.

The function of the sulphonic acid group is to impart hydrophilic properties, that is, water wetting or water attracting properties, to the molecule as a whole. The groups which are esterifled by the sulpho-carboxylic or sulpho-fatty acid are in general of a lipophile-character. At

times they may be strongly lipophilic and at other times moderately lipophilic. They may be of low molecular weight or of moderately high molecular weight, depending upon the purpose for which the substances may be used.

The lipophile groups entering into the molecular structure of my substances may be of simple character as, for example, in sulpho-acetates of straight chain alcohols such as hexyl alcohol,

octyl alcohol, decyl alcohol, lauryl alcohol and the like, or of similar lower molecular weight supho-carboxylic acid esters of branched-chain alcohols such as 2-ethyl hexanol-l, 2-butyloctanol-l, and the like.

Others 0! the substances of my invention are lower molecular weight sulpho-carboxylio acid esters or polyhydroxy substances, at least one esteriiied with a carboxylic acid containing at hydroxy group of the polyhydroxy substance being least four carbon atoms and prefersbly'between eight and eighteen carbon atoms. In addition to the compound mentioned above, other exampies of compounds falling'within the scope of my invention are as follows:

Ostyl other oi monostssrin suiphoooststo (sodium suit) (2) HsCO- Cu al o o H! olt-0154 0 Monolsutin mpmu (sodium mo ONo Monopslmitin sulphobutynts (sodium salt) 0 nic-o-r'-mm 0' 0 Ha 0 CH-S:0

' m om Mono-palmitic acid cstz a gt lzgneglyooi sulphooropionats ONs Di-sulphosoetic acid ester 0! mono-olsin (disodium salt) 0N: W odd of (up Mono-aisle acid do: otdisthylsns glycol sulplsoocgtsts (sodium salt) 037i mlphoocstots (sodium salt) (Butyi MW flyool sulphnmio (potassium silt) I v t C|lH- c-CHgS=O g ONs I Olly! lflpm (sodium I") 0 v (l8) OHPCH -CHg-GH -CHHgO-C-OkflO I sB's 0N. DIM on-diwi halal-i (sodium it) anon H=o-c -cn,-s=o

H ONa Mono-cetyl glycerol sulpho-acetate (sodium salt) ongo oum l V o Hz-C-C-CHz-SO ONa Lauryl glyc'ol-sulphoacetate (sodium salt) CHz-O-CxsHM non L nr o'ocnz-soax Bt aryhglycerol sulphoaeetate (potassium salt) 'I,may select many different types of com pounds 'as lipophile groups, particularly those having at least eight carbon atoms although, for

some purposes, the lipophile group or groups may contain as-low asfour carbon atoms. For example, thefollowing compounds may be utilized as sources of lipophile-groupsyand sulpho carboxylio acid esters thereof such as sulphoacetates may be prepared therefrom by procedures described more' fully hereinafter: butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, ricinoleyl alcohol, palmitoleyl alcohol, ricin-' oleic acid, hydroxy and a-hydroxy fatty acids such as a-hydroxy stearic acid, a-hydroxy laun'c acid, i-hydroxystearic acidya-hydroxy palmitic acid, and the like, ceryl alcohol, carnaubyl alcohol, myricyl alcohol, and, in general, thehigher molecular weight saturated and unsaturated aliphatic alcohols. Imay also employ cyclo-ali the sulphoacetates oftpure lauryl phatic or all-cyclic alcohols such as the starch. as, for example, cholesterol, iso-cholesterol, phytosterol, as well -as hydro-aromatic alcohols such as abietol. In addition, I may utilize such unsaturated alcohols as linalool, citronellol, ge- 5 raniol and the like. Itis, of course, obvious that the alcohols may be prepared in accordance with any desired method. For example, thesealco- I 1 hols may be prepared by the so-called Bouveault and Blane method or, alternatively, by the reduction or catalytic reduction with hydrogen of natural or hydrogenated animal or vegetable fats and oils in accordance with well known practices. Again, the alcohols maybe' derived from synthetic processes such as by the oxidation of hydrocarbons or maybe prepared bysa'ponification of waxes and the like. Alternatively,

, they may be prepared by reduction of aldehydes tlon in substantially the identical manner as the 30 sulpho-carboxylic acid esters of the substantially pure alcohols. Again, mixtures of alcohols such as arepresent in the so-called sperm oil alcohols, as well'as those present in wool-fat,

'may equally eificaciously beutllized. Indeed, 5

these higher-molecular weight alcohols are generally, if, indeed, not almost invariably, offered on themarket in the formof mixtures of diflerent alcohols. If desired for any specific purpose, special fractions which predominate in a certain 40 particular hig er molecular weight alcohol may I :be utilized or, so desired, the sulpho-carboxylic esters mayv be prepared from a single, substantially pure alcohol.v Since, obviously, for example, lauryl, alcohol is the "same'irrespective of how it isprepared, the sulphoacetates or the like -pre pared therefrom are the same andfunction/in, like'manner. Similarly, sulphoacetates of commercial mixtures of alcohols containing predominant amounts of, for example, lauryl alco- 5o hol, function essentially identically t e same as lcohol; It will be seen, therefore, that the source of the higher molecular alcohols from whiclr' my sulpho-carboxylic' esters are prepared is entire]? immaterial.

So far as the sulpho-carboxylic esters are concerned which are derivatives of polyhydroxy substances, I may select many. different types of compounds as lipophile groupswhich. are to be esterified with the polyhydroxy substances, principally compounds having lipophile radicals of relatively high molecular weight. For example, the following materials maybe utilized as sources a of lipophile groups: carbox'ylic or fatty acids such as but-yric acid,-caprylic acid, caproic acid, capric acid, saturated and unsaturated higher molecular weight aliphatic acids such as thehigherfatty acids containing at least eight carbon atoms and including melissic acid, stearic 'acid,'0leic acid, H) ricinoleic acid, linoleic acid, lauric acid, myristic I acid, palmitic acid, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, sesame oil, corn oil, cottonseed oil, sardine oil, partially or completely 4 hydrogenated animal and vegetable oils-"suchas those mentioned, fatty acids derived from various waxes such as beeswax, spermaceti, montan wax.- and carnauba wax and carboxylic -acidsderived,-.

by oxidation and other methods, from petroleum, hydroaromatic acids such as naphthenic acid, abietic acid, hydroxy aromatic acids, such as hydroxy benzoic acid, aromatic acids such as benzoic acid; naphthoic'acld, and the like.

The polyhydroxy substances whichprovide the linkage, between the lipophile group and thesul- I pho-carboxylic group may be selected from a largeuclass and include glycerol; glycols such as ethylene glycol, propylene, glycol, trimet'hylene glycol, butylene glycol and the likerpolyglycols such as diethylene glycol; polyglycerols such as diglycerol, triglycerol, tetraglycerol and the like including mixtures thereof; sugars such as dextrose, sucrose, xy1ose,- galactose, fructose, maltose, mannose and the like; sugar alcohols such as arabitol, mannitol, sorbitol and dulcitol; and polyhydroxy-carboxylic acids such as tartaric acid, mucic acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonic acid, trihydroxyglutaric acid, vglyceric acid, carboxylic oxidation products of polyglycerols, others of similar character, and hydroxyethyl and hydroxypropyl ether derivatives of the above, as for example: mo-b-om-cmon Bo-o-cnr-cmon (For convenience, all hydroxyl groups are;

written facing one way.) I In those of my compounds which are sulpho carboxylic esters of lipophile derivatives 01 polyhydroxy substances, the linkage between the ployhydroxy substance and the lipophile group need not be an ester linkage, although such is pre- .Ierred, but it may be an ether linkage, as illustrated by compounds numbered (14), (25), (26) and (27) hereinabove.

From a study of the compounds which). lis

hereinabove, those skilled in the art will understand that I may use many different expedients for forming the c'cmpounds in so far as the dominant lipophile group and the relatively low molecular' weight sulpho-fatty' acid group are concerned. As stated, however, ester linkages are fit utilized between these two portions of the com- I pound; and the skilled chemist'will understand in general the mostapp'roved practices in securing this result. Numerous methods are also available for the introduction oi the sulphonic acid group. In the case of aromatic sulphcuic acids,oi' course, standard sulphon'ation .procedures employed for producing aromatic sulphonic acids niaybe used, and, ii duired, the lipophile group may be introduced subsequently.

In the case ofaliphatic sulphonic acidaanp, tor

that matter, even-tor the production of aromati sulphonic' acids, a reactive halogen may be caused to react with sodium sulphite or potassium sulphite or ammonium sulphiteor some other sulphite in aqueoussolution, if desired,

Another method is to introduce a sulph-hydryl or disulphide or some other suitable sulphur group and then oxidize to the sulphonic acid with nitric acid or a permanganate or some other oxidizing agent.

other methods will suggest themselves to the skilled chemist. Thus, for example, one or more esterinable hydroxyl groups of a higher one. The sulpho-acyl halides may also be of the type wherein the sulphonic group is attached to an intermediate carbon instead of to the ter-- minal carbon as illustrated above.

Another method which may also be employed I to produce the compoundsmi my invention involves reacting a straight chain higher molecular weight alcohol or a polyhydroxy compound or derivative thereof, there being at least one free hydrox'y group present in the polyhydroxy nucleus, with a'sulpho-acyi anhydride the sulphonic group of which may be attached to either the terminal vor an intermediate carbon atom of the sulpho-- acyl anhydride. v I v t My preferred process comprises reacting a higher molecular weight alcohol, such as cetyl alcohol, or one or more free or,e steriilab le hy-. droxy groups of a polyhydroxy substance or derivative of a polyhydrcxy substance, with a hal-' ogeno-carboxylic acid such as chloracetic or bromacetic acid, or with a halogeno-carboxylic acid halide such as chloracetyl chloride or bromacetyl bromide, to form a chloracetat or bromacetate, and then converting the latter into. the

sulphonic acid derivative by reaction with an alkali metal sulphite.

The following examples are illustrative of the preparation or compounds falling within the scope of my invention. It will be understood that said examples are given only by way 01'' illustration and are not to be considered in any way limitativeof the true scope of my invention. Erma: I.Hmosteafine sulphoacetate, Na salt 7 (a) 700 parts of monostearine were heated with 1'15 parts or chloracetic acid for 3 hours at a temperature 01150-180 degrees C. in an atmosphere or CO: and with agitation. The reactionproduct was-washed free of chloracetic acid with 4 times its own volume oiwater at 95 degrees C. and,

to assist in separation, 100 parts oi salt were uided to thewashwater.

(6) The product obtained in' (a) was mixed with 500 parts oi. water, heated to about 60-degrees 0., and then 175 .parts of sodium sulphite were added. The temperature was maintained at 60-75 degrees C. with constant stirring for the first hour, then raised to 90-95 degrees. C. and kept at that temperature for about three-quarters of 'an'hmmv g 1 (c) To remove excess sulphite and other objectionable impurities, the product obtained in (b) was dispersed in Q times its own volumeoi water a white paste containing about 50%.water was obtained. The water may be eliminated in any desired manner to produce a dry product.-

; Exsxru: IIQ-Distearine sulphoacetate ture. A brittle substance which could easily be ground into a powder was obtained. It dispersed readily in water. Exam IlIL-Distearine sulphoacetate, K salt (it) 200 parts of distearine were heatedwith 65 parts of chloracetic acid for 3 hours at 160-170 degrees C. When the reaction was completed the product was washed free of chloracetic acid and dried.

a '(b) 50 parts of' the product obtained in (a) were mixed with 25 parts of potassium sulphite dissolved in 35' parts of water. 2 parts of potassium iodide were added and the mixture stirred and heated for about 10 hours on a water bath at 60-70 degrees C. and about 2 hours at 75-80 degrees C.

(c) To remove excess sulphite, 50 parts of the product obtained in (b) were dispersed in 500 parts of water, heated to 80 degrees C., and then salted out with 15% salt; The washing process was repeated several times. A paste containing about 50% water was obtained.-

(d) For further purification, 150 parts of iso-- propyl alcohol were added to 10 parts of the paste, .the mixture brought to the boiling point and filtered hot. The filtrate wasallowed to cool and the precipitate that came down filtered off,

washed several times with ether and then dried at room temperature. The product obtained dispersed readily in hot water.

Exnnma IV.-Monostearine disulphoacetate, K

' salt (a) 500 parts of monostearine wereheated with 500. parts of chloracetic acid at a temperature of 160 degrees C. for several hours using a stream of CO: for the p p se of agitation and toremove water of reaction; The heating was continued until the chlorine content correspond-= -ed to approximately 100% of monostearine dichloracetate. i I

(b) 35 parts of the washed and dried product obtained in (a) were mixed with 25 parts potassium sulphite in-40: parts of water. 4 parts of potassium iodide were added and the mixture stirred and heated on a water'bath for about 8 hours at 70-80 degrees C.

(c) The product obtained in (b) was dispersed in 400 parts of water at 60-70 degrees C. and the dispersion saturated with sodium chloride. Very little separation took place. 0n chilling in an ice bath to 10 degrees C., the product could be isolated by gravity filtration. The process or dispersion, saturating with salt, chilling and grav- 'ity filtration was repeated a second and third time. A white paste containing about 50% water was obtained. e

(d) To further purify the product obtained in (c) parts of, the latter were dispersed in 10 parts of water. 80 parts of hot isopropyl alcohol were added and the mixture brought to the boiling point and then filtered hot. on cooling and by the addition of a little more isopropyl alcohol,

the sulphoacetate was precipitated. The precipitate was filtered oil and dried at room tempera.-

ture.

EXAMPLE V.-Monostearic acid ester of diethylene glycol sulphoacetate, K salt .(a) 500 parts of diethylene glycol monostearate, prepared by heating a mixture of one part of stearic acid with one part of diethylene glycol at a temperature of about220 degrees C., using 0.1% KOH until the free fatty acid content is down to about to 1%, was heated with 250 parts of chloracetic acid at 160-170 degrees C. for 4 hours. The product was washed freeof chloracetic acid and dried.

(b) 50 parts of the product obtained in (a) were mixed with 35 parts of potassium sulphite and 50 parts water. 2 parts of potassium iodide were added and the mixture stirred and heated for-about 10 hours at 70-75 degrees C. At the end of the 10 hours, 800 parts of hot isopropyl alcohol were added, the mixture brought to the boiling Point and filtered hot. The alcohol solution was allowed to cool. The product was obtained in the form of a precipitate consisting of crystals of grayish leaflets. These dissolved readily in hot water.

Exmns VI.-C'oconut mono fatty acid esters of diethylene glycol sulphoacetate, K salt (a) '400 parts of the fatty acid mono esters of diethylene glycol with mixed coconut oil fatty I acids were heated with 260 parts of chloracetic acid for 3 hours at 160 degrees C. using a stream of CO1 for agitation and removal of moisture.

(b) 200 parts of the washed and dried product obtained in (a) were mixed with 130 parts of potassium sulphite and200' parts 01' water. 4 parts of potassium iodide were added'and the mixture stirred and heated on a water bath at '60-70 degrees C. for about 10 hours. The reaction product was then dispersed in about 8 times its own volume of water heated to -70 degrees C. and salted out with 15% salt. The washing was repeated a second and third time. A thin paste, light in color and containing 60% water was obtained.

(c) The product may be used as finally obtained in (b) or may be purified by heating to the boiling point with 8 volumes of isopropyl alcohol, filtering hot and allowing the alcohol solution to cool. The precipitate which comes down is illtered oil and dried at room temperature. The filtrate may be evaporated to dryness to recover the alcohol soluble substances.

Exmu: TIL-Cholesterol sulphodcetate, Na salt (a) Qparts by weight of cholesterol, 9 partsby weight of brom acetyl bromide, and 40 parts by weight of benzene were heated under a reflux condenser for two hours at the'boiling point or dissolved in 40 parts of hot water, the mass being heated for five hours at about 100 degrees C.

with continuous, vigorousagitation.

to) The above reaction mixtures was then washed several times with hot brine, until free of sulphites, dried, and finally purified by extracting the impurities with dry ethyl ether, An'

I analysis showed that the final product was cholesteryl sulphoacetate, sodium salt, containing a small percentageof sodium chloride.

Exams: VIIL-Mono-lauryt glycerol sulphoacetate, Na salt drochloric acid, was then'mixed with 1000 grams bf sodium sulphite dissolved in 5000 cc. of'water and heated to between '75 degrees C. and 85 derees C. for one and one-hali hour with constant stirring.

The resulting product, mono-lauryl glycerol sulphoacetate, Na salt ONa V I was recovered in purified form in substantially the same manner as described in the above examples.

Eximru: lxr aetyl ethylene glycol sulphoacetate, K salt g 136 grams of the cetyl etherof ethyleneglycol chloracetate 1 were mixed with 155 gramsof potassium sulphite dissolved in 275 cc. of water and the mixture was heated at 85. degrees C. for about one and onehalf hours.

} -'Ihe resultingproduct was freed of potassium chloride in ,substantiallythe manner set forth in the above examples. 1

Exam ne X.Laurvl sulphoacetate, K and Na salts (al 500 grams of lauryl alcohol and 2 grains of chloracetic acid were heated ,together for two. hours at 140 degrees C. to 150 degrees C. inan atmosphere-of carbon dioxide gas. The reaction product was then washed freelofexcess chloracetic acid and, if desired, may be dried over anhydrous'sodium sulphate.

(b) 520 grams of the lauryl cbloracetate prop duced as described in part (a) .were mixed with 410 grams of.anhydrous potassium sulphite dissolved 111.550 cc. of water and the entire mass ,was stirred vigorously and heated'iorfour hours v at- 95 degrees C. to 97 degrees C, If desired, the reaction may be facilitated by the addition to the reaction mass of 5 grains ofpotassium iodide or 2 to.3.gramsof laurylrpotassium sulphoacetate or a mixture of'both the iodide andthe suiphoacetate. When the reaction was completed, the

' "resulting mass was poured intog25 00 cc. ofcold.

lauryl potassium sulphoacetate was filtered oil.

(c) I! it is desired toiurther purify the product, it maybe dissolved in hot water degrees 5 C. to degrees 0.), to make approximately a 10% solution and the solution may; then be cooled to 20 degrees C., at which temperature practically all of the lauryl potassium sulphoacetate crystallizes out, The crystals may then be filtered 10 oil and dried. They are of white, flufiy character.

(d) To prepare lauryl sodium sulphoacetate.

the reaction was carried, out in the same way as described in (b)' except that the following proportions'of ingredients were employed: 15 Lauryl ohloracetate grams 500 sodium uilphitn' v do 365 Water r cr 500 (e) Because of the greater solubility of the 20 sodium salt of lauryl sulphoacetate than that of the potassium salt, it is somewhat more difiicult ,to isolate the former. In the present case, the reaction mass or part (d) was mixed with between 5 and 6 volumes of hot water (80degrees C.- to 90 degrees C.) and was heated and stirred until essentially completely dispersed. About 15% of common salt was .then added and the entire mass was then chilled and filtered. The dispersidn in hot water and the salting-out operation 30 were repeated to times. The paste which was I obtained was then dried. It could be still further purified by admixture .with 10 volumes of hot isopropyl' alcohol, filtering, and cooling the alcohol solution to cause the lauryl sodium sulphoacetate to crystallize out.

'Exsmuin XL-Stearyl potassium sulphoacetate (a) Stearyl chloracetate was, prepared as described in Example x (a), 'usingthe' following proportions of ingredients:

. I I Grams Stearyl alcohol 500 Chloracetic acid .250

(12) 500- grams of stearyl chloracetate, as pre- 4 pared in (a), were mixed with 350 grams of anhydrous potassium sulphite, dissolved in 600 cc.

of water with or without the addition of 5 grams of potassium iodide. The mixture was stirred vigorously and heatedfor four hours at de- 50 grees C. I

(e) 'The resulting reaction mixture was then poured into between 3 'and 4 volumes of hot water (80 degrees C. to 90 degrees C.) and between 10% and 15% of common salt were added- 55 to sa t out the stearyl potassium sulphoacetate.

Theaddition of hotwater and the salting-out operation were repeated three times and the final paste obtained was dried and ground into a powder. By dissolving in isopropyl alcohol and crystallizing out therefrom, 'as described in Example X, a crystalline'product was obtained.

Exmrrr XII. (.'.'etul' (palmityl) potassium sulphoacetate r (a) The procedure described in Example X was followed employing 325'grams of cetyl alcohol andv grams of chloracetic acidfor the preparation of the cetyl chloracetate; and 350 grams of cetyl chloracetate, .300 grams of anhydrous potassium 7 of the cetyl potassium sulphoac'etate.

'(b) The purification of the cetyl potassium sulphite and 400 cc. of water in the preparation 'sulphoacetate after obtaining the crude filter cake, as described in Example X, was carried t water, with stirring, and the mixture cooled to 20 degrees C.-, whereupon the crude ing '70 arcane crystallizing out, whereupon it was filtered oif and "dried.

EXAMPLE XIII.-Decyl potassium sulphoacetate (a) Decyl chloracetate was prepared by admixthe decyl chloracetate then being washediree of acid. The benzol was removed by distillation.

(b) 60 grams of decyl chloracetate were mixed with a solution containing 50 grams of anhydrous c. When the reaction potassium sulphite, 0.5 and 100 cc. of water, heated, with stirring,

gram of potassium iodide,

for 4 hours at 95 degrees was complete, 1000 cc. of water were added whereupon a substantially clear solution was obtained. The solution was then chilled to between degrees C. and degrees C., the decyl potassium sulphoacetate crystallizing out. It was filtered off and dried, a white, crystalline powder being obtained.

EXAMPLE XIV.-p-ethyl hezcyl potassium sulphaacetate (a) The chloracetate oi fi-ethyl hexyi alcohol was prepared as described in Example XIII (a),

using the following proportions of ingredients? fi-ethyl hexyl alcohol grarns '77 Chloracetyl chloride do 70 Benzol cc 75 (b) 85 grams of fl-ethy] hexyl chloracetate were mixed. with a solution of 130 grams of anhydrous potassium sulphite and 2 grams of potassium iodide in 200 cc. of water and the resulting mixture was heated for between-5 and 6 hours at 90 degrees C.

(c) When the reaction-was completed, 100 cc. of hot water were added to the reaction mass and it was then chilled to degrees C. p-ethyl hexyl potassium sulphoacetate which crystallized out was, when filtered out and dried, a white powder.

EXAMPLE XV.-H1 drogenated citronellol potassium sulphoactate (a; 50 grams of hydrogenated citronellol were heated with 50 grams of chloracetyl chloride for about 4 hours at 80 degrees C, or until'there was no further evolution of hydrochloric acid. The excess chloracetyl chloride was decomposed by the addition of water and the hydrogenated citronellol chloracetate was washed free of-chioracetic acid. g

(b) grams of hydrogenated citronellol chloracetate were mixed with a solution of 25 grams of anhydrous potassium sulphite dissolved in 26 cc. of water. The mixture was heated, with stir-. ring, for about 5 hours or until a substantially clear solution was obtained. The stirring and heating were then continued for another hour whereupon 600 cc. of boiling isopropyl alcohol were added. The solution was then filtered to remove inorganic salts and the filtrate was evaporated to dryness. The product thus obtained was then treated with ether to remove any fatty sub stances which might be present.

Those skilled in the art are referred to my The mixture was their molecular weight monosulpho-carborwlic acid, Y is a cation,

Patent No. 1,917,260, which I disclose the use of some of. the compounds of my present invention ing some of these, compounds.

Those of my substances which are freely soluble tures ranging from he form of a paste with from approximately 25 The more hydrophilio the substance,

a water content ranging to 75%.

was salted out.

Many of the compounds of my invention may be represented by the general formula R-COO-R1 wherein R denotes a lower molecular weight aliphatic radical containing at least one sulphonic acid radical and R1 denotes a radical of a higher or polyhydric alcohol.

Many of the compounds of my invention may also be represented by the general formula my invention represented by the following general wherein R, ;is the residue of. a polyhydroxy substance in which the hydrogen of at least one hydroxyl group is substituted by an alkyl or. acyl group containing at least four carbon atoms and preferably between eight and eighteen carbon atoms, X is the carbon-hydrogen. residue of the and w is a small whole number, at least one.-J

I have previously referred to the factthat the lipophile group may in itself contain hydrophile radicals. For example, in the case of monostearln sulphoacetate, the hydroxy radical of the second glycerine carbon has a. recognized hydrophilic character. The groupasawho1e,-however, of

. which this hydroxy radical is a. part, is domi- 60 to 95 degrees C., the sub- I stances are obtained in and preferably from twelve to eighteen carbon 8 v I v I M tached to the sulphonic acid group by esteriflcation. When the character R. is used in the formula, therefore, to represent a llpophile group, it is with the assumption that the group as a whole does .not possess a hydrophilic character.

In so far as the sulpho-carboxylic or sulphofatty acid group of my compounds is concerned, may employ a sulpho-acetate, sulpho-proplonate, sulpho-butyrate, or other siinilar groups containing an unesterified sulphonic acid radical and, Y generally, not more than seven carbon atoms. In general, however, I have found that the sulphoacetates particularly produce compounds 01 ex- :eptionally valuable characteristics and theyhave the advantage of being relatively inexpensively produced from commercially available substances. The terms sulfo-carboxylic acid" and "sulpho fatty acid as employed throughout the specification and claims are used ina strictly rigorous. sense to mean an aliphatic compound which con-. tains at least one When prepared by other methods so that the" compounds contain the sulphonic acid group (-SOaH) the hydrogen thereof may be replaced by other cations such as calcium, magnesium,-

sluminum, zinc, amines, alkylolamines such as mono-, diand triethanolamine and mixtures thereof, other organic nitrogenous bases such as pyridine and" piperidine,.tertiary amines, quaternary ammonium bases, etc. It will be understood that by the term cation, as used throughout the specification and claims, is'meant hydrogen and-such other elements as are mentioned herein, and in general. atoms or radicals which are regarded as hearing a positive charge or capable of replacing acidic hydrogen. I

It will be understood that the selection of the particular halogen derivatives which" are utilized in the preparation of the halogen-carboxylic acid ester intermediate. products will depend upon certairipfactors Thus, while bromoand iodo- I derivatives, in general, react slightly more rapidly than do the chloroderivatives, therelatively cheaper cost of the latter will generally justify their use from apurelyeoonomic standpoint}.

My resent application is a coIitinuation-in-. part 0! my copending applications, Serial No.

34,840,1iled August 5.1935, and Serial No. 1

filed January 21, 1937, which'applications are continuatiohs-in-part of my application, Serial No. 627,096, flied July.30, 1932. .-.-This latter application is in turn a continuation-inpart or my application Serial No. 481,349, filed September 11, 1930, now Patent No. 1,917,255, which'was a continuati'on-i'n-part oimy prior-application Serial No. 475,622, filed August 15, 1930, now Patent No. 1,917,250.

The term "residue, as. used-throughout"the specification and claims, is employed in its on dinarily understood chemical significance. For,

example, where one of the-hydroxyl groups of .,corresponding to the general formula V glycerine is esteriiied with a fatty'acid and another of the hydroxyl groups of the glycerin'e is esterifled with a sulpho-carboxylic acid, that "which remains oiflthe glycerlne molecule, for example CH|-- k mon is the residue of the polyhydroxy substance, in this case gly'cerine.

Similarly, the term fcarbon-hydrogen residue of asulpho-carboxylic acid isqemployed as inconventional chemical nomenclature. Thus, for

example, if 'sulpho-acetic acid (nooc-cm-soirr) is esterined with glycerine, the group CH:--,- is

. to be considered as the carbon-hydrogen residue of the sulphmacetic acid.

" It-will be understood that the term lipophile group, as employed herein, is intended to cover any radical containing at least four carbon atoms and having an aifinity i'or oleaginous material such as-oils, fats, hydrocarbons and the like and may comprise radicals such as hydrocarbon radiand the like. The hydrophile group or groups, in other words, the groups having an aiilnity for aqueous materials. are, as iully set forth hereinabove, sulpho-carboxylic or sulpho-fatty acid groups.

Unless otherwise indicated, the term higher, wherever employed in the claims, will be understood to mean at least eight carbon atoms and,

concomitantly, the term lower" will mean less than eight carbon atoms.

Whenever the term sulphocarboxylic ester,

sulpho-acetate, or the like expression is employed in the claims, it will be understood to cover. the

' cals, acyl or alkylgroups derived. from aliphatic" a or fatty acids or their corresponding alcohols,

compounds irrespective of whether the hydrogen placed by another cation.

What I c'laim as new and desire toprotect b Letters Patent of the UnitedStates is:

' of the sulphonic acid is present as such or re- 1. Sulpho-carboxylic ,esters, suitable for; use

as assistants in the textile and related industries, corresponding to the general formula in which, R denotes an aliphatic radical, containing up to '7 carbon atoms and at least one sulphonic' radical, and R1 denotes a radicah oi an. aliphatic alcohol containing at least 8 carbon atoms.

2. Sulpho-carboxylic esters, suitable for as assistants in the textile .and related industries,

in which R denotes an aliphatic radical, steam-1 ingup to 7 carbon atoms and at least one sulgphcnic radical, and R; denotes a radical of an aliphatic alcoholcontaining irom 12 to18 carbon atoms.

. 3. Sulpho-acetates oi aliphatic alcohols containing atileast 8 carbon atoms, suitable iora use asassistjants in the textile'and related industries.

1. 4': Sulpho-a'cetates of aliphatic alcohols con- -taining irom 12 to 18 carbon atoms, suitable for 5. Sulpho-carboxylicesters; suitable for use as assistants'in the textile and related indus-. ,tries.

wherein R contains a lipophile group with at least arcane r 9 assistants in the textile and related industries, corresponding to the generalformula 7 in which R denotes a; sulpho acetic .acid radical and R1 denotes a radical of a high molecular weight unsaturated alcohol.

6; A lower molecular weight sulpho-carboxylic acid ester represented by the general formula four carbon atoms, X is the carbon-hydrogen residue of the lower molecular weight sulpho-carboxylic acid, Yis a cation, and w is'a small whole number, at least one.

7. Sul'pho-carboxylic esters, suitable for use 'I as assistants in the textile and related industries, corresponding to the general formula in which R denotes an aliphatic radical contain ing' up to 7 carbon atoms and at least one sulphonic radical, and R1 denotes a radical of a high molecular weight unsaturated alcohol.

8. Esters of lower molecular weight sulpho fatty acids and higher aliphatic alcohols.

9. Lauryl sulphoacetate. 10. Cholesteryl sulphoacetate.

11. A carboxylic ester of a lower molecularweight sulpho-fatty acid having at least one unesterifled sulphonic acid group, and wherein the radical esterified with the sulpho-fatty acid includes a lipophlle group with at least four carbon atoms.

12. A lower molecular weight sulpho-fatty acid ester of an aliphatic alcohol containing at least !our carbon atoms.

, 13. A sulpho-acetic acid ester of an aliphatic I alcohol containing at least four carbon atoms.

14. The process which comprises reacting, a

a halogen-containnlg ester of a higher molecular weight unsaturated alcohol and a lower aliphatic 'monocarboxylic acid, the halogen being attached to the alkyl portion of the acyl group,' with an alkali metal sulphite whereby the halogen is re placed by a sulphonic acid radical.

15. The process which comprises reacting a halogen-containing ester of a higher molecular weight alcohol and a lower aliphatic monocarboxylic acid, the halogen being attached to the alkyl portion of the acyl group, with an alkali metal sulphite whereby the halogen is replaced by a sulphonic acid radical.

'16. The process which comprises reacting a higher molecular weight aliphatic alcohol with a lower halogen -containlng aliphatic monocarboxylic acid derivative whereby a halogen-containing ester is produced, and then reacting the resuiting ester with an alkali metal sulphite whereby the halogen is replaced by a sulphonic acid radical. I 17. The process which comprises reacting an alcohol containing at least eight carbon atoms.

19. A chemical substance represented by the general formula wherein R is a llpophile group with at least four carbon atoms, XCO is the acyl radical of a lower sulpho-fatty acid, Y is a cation and w is a small whole number, at least one.

20. A lower molecular weight sulpho-carboxylic acid ester of an alcohol containing at least four carbon atoms.

. 21. A lower molecular weight sulpho-carboxylic acid ester of an alcohol containing at least four carbon atoms, a sulphonic group of said sulphocarboxylic acid radical being connected to the same carbon atom to which a. carboxyl' group of said sulpho-carboxylic acid radical is connected.

22. A lower molecular weight sulpho-carboxylic acid ester of an aliphatic alcohol containing at least four 'carbon atoms, a. sulphonic group of said sulpho-carboxylic acid radical being connected to the same carbon atom to which a carboxyl group of said sulpho-carboxylic acid radical is connected.

23. A lower molecular weight aliphatic carboxylic acid ester of a higher molecular weight alcohol, a sulphonic radical being attached to a carbon atom of the lower molecular weight aliphatic carboxylic acid radical. I

24. The process which comprises reacting a compound having a lipophile group with at least four carbon atoms and at least one esterifiable hydroxy group with a member selected from the group consisting of lower molecular weight halogeno-carboxylic acids and derivatives thereof to producea halogeno-carboxylic acid ester of said first-mentioned compound, and then reacting the resulting ester with an alkali metal sulphite whereby the halogen is replaced by a sulphonic radical.

25. The process which comprises reacting an aliphatic alcohol containing at least four carbon atoms and at least one esterifiable hydroxy group with a member selected from the group consisting of lower molecular weight aliphatic halogenocarboxylic acids and derivatives thereof to produce a halogeno-carboxylic acid ester of said alcohol; and then reacting the resulting ester with an alkali metal sulphite whereby the halogen is replaced by a sulphonic radical.

26. Lower molecular weight sulpho-carboxylic acid esters of lauryl alcohol. BENJAMIN R. HARRIS. 

